N-cyclopropylmethyl halo-acetamides

ABSTRACT

Compounds characterized by the following structural formula:   WHEREIN R is one selected from the group consisting of Y-CH2 and   Y is one selected from the group consisting of chlorine, bromine and fluorine, X is one selected from the group consisting of hydrogen, chlorine, CF3, C1 to C4 alkyl, bromine, C1 to C4 alkoxy, and C1 to C4 alkylthio, and X&#39;&#39; is one selected from the group consisting of chlorine, hydrogen, CF3, and bromine; R1 is C3 to C4 cycloalkyl optionally substituted with C1-C3 alkyl, chlorine, bromine, R2 is one selected from the group consisting of hydrogen, and C1 to C4 alkyl, cyclopropyl, cyclopropylmethyl and C1 to C3 alkoxy, and R3 is one selected from the group consisting of hydrogen, C1-C3 alkyl, cyclopropyl, cyclobutyl, cyclopropylmethyl or cyclobutylmethyl, optionally substituted with C1 to C3 alkyl, chlorine, and bromine; n is either 0 or 1. These compounds have been found to possess biological activity and have been found to be useful as herbicides.

1111 memes 1 Dec. 2d, 197% N-CYCLUPQPYLMETHYL l-llALO-ACETAMKDES [75]Inventor: Lester L. Maravetz, Westfield, NJ.

[73] Assignee: Esso Research and Engineering Company, Linden, NJ.

[22] Filed: Feb. 12, 1973 [21] Appl. No.: 331,722

Related US. Application Data [62] Division of Ser. No. 58,672, July 27,1970, Pat. No.

[52} 11.8. C1. ..260/561HL, 71/98, 71/118, 71/120 [51] int. Cl. C07C103/30 [58] Field of Search 260/561 HL [561 1 References Cited UNITEDSTATES PATENTS 3,007,786 11/1961 Hamm et a1 260/561 HL 3,356,724 12/1967Olin 260/561 HL 3,471,522 10/1969 Biel et al 1 260/347.7

3,532,712 10/1970 Biel 6i al. 1 1 260/561 HL 3,532,749 10/1970 Biel eta]. 260/561HL 3,646,146 2/1972 Teotino et al. 260/561 HL PrimaryExaminer-Lewis Gotts Assistant Examiner-Ethel G. Love Attorney, Agenz,0r Firm-Frederick H. Rabin 1 ABSTRACT Compounds characterized by thefollowing structural formula:

R C N (CH R wherein R is one selected from the group consisting of Y--CHand Y is one selected from the group consisting of chlorine, bromine andfluorine, X is one selected from the group consisting of hydrogen,chlorine, C1 C to C alkyl, bromine, C to C all oxy, and C, to C,alkylthio, and X is one selected from the group consisting of chlorine,hydrogen, C1 and bromine; R is C to C,, cycloalkyl optionallysubstituted with C -C alkyl, chlorine, bromine, R is one selected fromthe group consisting of hydrogen, and C, to C alkyl, cyclopropyl,cyclopropylmethyl and C, to C alkoxy, and R is one selected from thegroup consisting of hydrogen, C -C alkyl, cyclopropyl, cyclobutyl,cyclopropylmethyl or cyclobutylmethyl, optionally substituted with C, toC alkyl, chlorine, and bromine; n is either 0 or 1.

These compounds have been found to possess biological activity and havebeen found to be useful as herbicides.

7 Claims, No Drawings 1 N-CYCLOPRUPYLMET This is a division ofapplication Ser. No. 58,672, filed On July 27, 1970, now U.S. Pat. No.3,728,386.

This invention relates to N-cycloalkylalkyl and N cycloalkyl substitutedphenyl ureas. In another aspect this invention relates to N-cycloalkyland N- cycloalkylalkyl halo acetamides. In yet another aspect, thisinvention relates to employing either the N- cycloalkylalkyl orN-cycloalkyl substituted phenyl ureas or the halo acetamides asherbicides.

Compounds possessing the following structures CH NHCN/ Monuron and Clmula are known to be herbicidal agents, where X F, Cl, Br, I,

R XCH CN A I and R and R are H, alkyl, alkenyl, alkynyl or halogensubstituted derivatives thereof. These types are described in U.S. Pat.No. 2,864,683.

However, none of the above mentioned prior art makes mention ofcyclopropyl or .cyclobutyl substituted derivatives.

HYL HALO-ACETAMIDES I It is generally known that larger ring systems arerelawherein R is one selected from the group consisting of Y CH and Y isone selected from the group consisting ofchlorine, bromine and fluorine,X is one selected from the group consisting of hydrogen, chlorine, CF Cto C alkyl, bromine, C to C alkoxy, and C to C alkylthio, and X is oneselected from the group consisting of chlo rine, hydrogen, C1 andbromine; R is-u C to C, cycloalkyl optionally substituted with C,-Cztlkyl. chlorine, bromine, R is one selected from the group consistingof hydrogen, and C to C, alkyl, cyclopropyl, cyclopropylmethyl and C toC alkoxy, and R is one selected from the group consisting of hydrogen,C,-( alkyl, cyclopropyl, cyclobutyl, cyclopropylmethyl or cyclobutylmethyl optionally substituted with C, to C alkyl, chlorine, andbromine; n is either 0 or 1.

' Examples of novel compounds which are encompassed by the'above genericformula are the following:

Compound 3-Phenyl-l-cyclopropylmethylurea 23-Phenyl-l-cyclopropylmethyl-l-methylurea 33-Phenyl3cyclopropylmethyl-l.l-dimethylurea 4 3(3,4-Dichlorophenyl)-3-cyclopropylmethyl-l,l

dimethylurea 5 3-PhenyI-3-cyclopropyl-l,l-dimethylurca 63-(4-chlorophenyl)-l-cycloprop'yLl-methy|urea 73-(4-chlorophenyl)-l-cyclopropylmethyl-l-methylurea 83-(3,4-Dichlorophenyl)-l-cyclopropylmethyl-lmethylurea 93-(3-Trifluoromethylphenyl)-l-cyclopropylmethyl-lmethylurea 103-(3,4-Dichlorophenyl)-l-cyclopropylmethyl-l-npropylurea ll3-(4-BromophenyU-l-t l-methylcyclopropylmethyl)-lmethoxyurea 1 I23-(4-Bromophenyl)-l l-methylcyclopropylmethyl)-lmcthylurca l33-Phcnyl-3-(2-n-propylcyclopropylmethylH-methylurea 143-(3-chloro-4-methylphenyl)-l-(2,2-dichlorocyclopropylmethyU-lmethylureal5 3-(4-methoxy-n-propylphenyl)-l-cyclobutylmethyl lmethylurea 163-(3-Chlor0-4-methylthiophenyl)-l-cyclobutylmcthyll-methoxyurea l73-(3-n-Butylthio-4-trifluoromethylphenyll-l-cyclobutyl-l'methoxymethylureal8 3-(4-chlorophenyl)-l-cyclobutylmethyl-l-n butylurea l93-(3-Bromo-4-methoxyphenyll l-cyclobutylmethyl-l methylurea 203-(4-n-Butylphenyl)-3-(Z-bromocyclobutylmethyl)-lmethylurea 213-Phenyl-l-cyclopropyl-l-cyc|opropylmethylurea 23N-Cyclopropyl-N-mcthyl-a-chloroacetamidc 24N-cyclopropylmethyl-N-ethyl-a-chloroacetamide 25 N-cyclopropylmethylN-n-propyl a-chloroacetamide 26N-cyclopropylmethyl-Nn-butyl-a-chloroacetamide 27N-cyclopropylmethyl-NJswpropyl-a-chloroacetamide 28N-cyclopropylmethyl-N-n-propyl-a-bromoacetamide 29N-cyclopropylmethyl-N-ethyl-a-fluoroacetamide 30 N-(l-mcthylcyclopropy|methyl )-N-ethyl-achloro acetamide 31N.N'bis(cycl0propylmethyl )-achlor0acetamide 32N-cyclopropyl-N-cyclopropylmethyl-a-bromoacetamide 33N-(2.2-dichlorocyclopropylmethyl)-N -n-propy|achloroacetamidc 34 Ncyclobutylmethyl-N-ethyl-a-chloroacetamidc 35N-cyclobutyl-N-n-propyl-a-chloroacetamide 36N-cyclopropylmethyl-N-2-methoxyethyl-a-chloroacetamide 37N-cyclopropylmethylN-allyl-a-chloroacetamide The foregoing compounds canbe readily prepared by the following synthetic method.

The ureas of this invention may be prepared by such conventional methodsas illustrated by the following equations where the various groups arethe same as indicated previously.

haloacetic anhydride reacts with the amine either neat or in solvent toform the product. Suitable solvents for 2 3 2 A. x@uco H-N l x NHCH\ 1(CH R (ca R x 2 n x 2 n o O u 2 B. x NH R2\ 2 5)3 X@-NCN\/R l l N-C-Cl(CH R x R l x R R- (can +(C2H5)3N-CHJ 9 R2 c 'x NH 0001 x NC-Cl H-N x Rx R l 1. 2 X@NCN: l

I X1 R3 (CH R Method A involves the reaction of an arylisocyanate 'withan amine usually in chemically equivalent amounts to give thecorresponding substituted urea. In method B, an aniline reacts with acarbamoyl chloride to yield the urea. A tertiary amine such astriethylamine, dimethylaniline, or pyridine may be used as an acidacceptor. Method C involves the reaction of an aniline with phosgene toform the intermediate carbamoyl chloride. This reactive compound is thenreacted with an amine to form the urea.

In all these reactions inert solvents such, as benzene, toluene, xylene,diethyl ether, chlorinated hydrocarbons, dioxane, dimethylformamide,acetonitrile and the like may be used to advantageif desired. Usuallytemperatures ofO to 150C. are sufficient for the above reactions.

The haloacetamides of this invention may also be prepared via knownmethods.

ln method D an a-haloacetylchloride is reacted with an amine in thepresence of a base such as NaOH, KOH, NaHCO etc., to formthecorresponding substituted a-haloacetamide. Usually lower temperaturese.g.. l0 to 30C. are employed to avoid the reaction of the amine withthe a-halo atom. ln method E. a

these reactions are the same as listed for the ureas.

30 The novel cyclic amines YCH CN (CH R pared by admixing one or more ofthe active ingred ients defined heretofore, in herbicidally effectiveamounts with a conditioning agent of the'kind used and referred to inthe art as a pest control adjuvant or modifier to provide formulationsadapted for ready and efficient application to soil or weeds (i.e..unwanted plants) using convention applicator equipment.

Thus, the herbicidal compositions or formulations are prepared in theform of solids or'liquids. Solid compositions are preferably in the form.of granulars or dusts.

The compositions can be compounded to give homogeneous free-flowingdusts by admixing the active comdiluent. Such diluents as natural clays,pyrophyllite, di-

atomaceous earth, flours such as walnut shell, as well as granular sandcan be employed.

In addition, granulars can also be compounded by admixing the activeingredient with one of the powdered diluents described hereinabove,followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual way byadmixing one or more of the active ingredient with a suitable liquiddiluent medium. In the cases where the compounds are liquids, they maybe sprayed in ultra low volume as such. With certain solvents, such asalkylated naphthalene or other aromatic petroleum solvents, dimethylformamide, cyclic ketones, relatively high up to about 50% by weight ormore concentration of the active ingredient can be obtained in solution.

The herbicidal compositions of the invention whether in the form ofdusts or liquids, preferably'also include a surface-active agentsometimes referred to in the art as a wetting, dispersing, oremulsifying agent. These agents, which will be referred to hereinaftermore simply as surfaceactive dispersing agents, cause the compositionsto be easily dispersed in water to give aqueous sprays which, for themost part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic,cationic, or nonionic type andinclude, for example, sodium and potassiumoleate, the amine salts of oleic acid, such as morpholine anddimethylamine oleates, the sulfonated animal and vegetable oils, such assulfonated fish and castor oils, sulfonated petroleum oils, sulfonatedacyclic hydrocarbons, sodium salt of lignin sulfonic acid (-goulac),alkylnaphthalene sodium sulfonate, sodium salts of sulfonatedcondensation products of naphthalene and formaldehyde, sodium laurylsulfate, disodium monolauryl phosphate, sorbitol laurate,pentaerythritol monostearate, glycerol monostearate, diglycol oleate,polyethylene oxides, ethylene oxide condensation products with stearylalcohol and alk ylphenol, polyvinyl alcohols, salts, such as the acetateof polyamines from reductive amination of ethylene/carbon monoxidepolymers, laurylamine hydrochloride, laurylpyridinium bromide, stearyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride,lauryldimethylamine oxide, and the like. Generally, the surface-activeagent will not comprise more than about 5 to percent by weight of thecomposition, and in certain compositions the percentage will be 1percent or less. Usually, the minimum lower concentrationwill be 0.1percent.

The herbicidal compositions are applied either as a spray, granular or adust to the locus or area to be protected from undesirable plant growth,commonly called weeds, i.e., plants growing where they are not wanted.Such application can be made directly upon the locus or area and theweeds thereon during the period of weed infestation in order to destroythe weeds, or alternatively, the application is made in advance of ananticipated weed infestation to prevent such infestation. Thus, thecompositions can be applied as aqueous foliar sprays but can also beapplied as sprays directly to the surface of the soil. Alternatively,the dry powdered compositions can be dusted directly on the plants or onthe soil. 4

The active compound is, of course, applied in an amount sufficient toexert the desired herbicidal action. The amount of the active compoundpresent in the compositions as actually applied for destroying orpreventing weeds will vary with the manner of application, theparticular weeds for which control is sought, the purpose for which theapplication is being made, and

like variables. In general, the herbicidal compositions as appliedin theform of a spray, dust or granular, will contain from about 0.1 topercent by weight of the active compound.

Fertilizer materials, other herbicidal agents, and other pest controlagents such as insecticides and fungicides can be included in theherbicidal compositions of the invention, if desired.

The term carrier or diluent as .used herein means a material, which canbe inorganic or organic and synthetic or of natural origin, with whichthe active ingredient is mixed or formulated to facilitate its stor-,age, transport, and handling and application to the plants to betreated. The carrier is preferably biologically and chemically inertand, as used, can be a solid or fluid. When solid carriers are used,they are preferably particulate, granular, or pelleted; however, othershapes and sizes of solid carrier can be employed as Well. Suchpreferable solid carriers can be natural occurring minerals althoughsubsequently subjected to grinding, sieving, purification, and/or othertreatments including, for example, gypsum; tripolite; diatomaceousearth; mineral silicates such as mica, vermiculite, talc, andpyrophyllite, clays of the montmorillonite, ka olinite, or attapulgitegroups; calcium or magnesium limes, or calcite and-dolomite; etc.-Carriers produced.

synthetically, as for example, synthetic hydrated silica oxides andsynthetic calcium silicates can also be used,

and many proprietary products of this type are available commercially.The carrier can also be an elemental substance such as sulfur or carbon,preferably an activated carbon. If the carrier possesses intrinsiccata-' lytic activity such that it would decompose the activeingredient, it is advantageous to incorporate a stabilizing agent, asfor example, polyglycols such as diethylene glycol, to neutralize thisactivity and thereby preare natural or synthetic resins such as acoumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride,styrene polymers and copolymers, a solid grade of polychlorophenol suchas is available under the registered trademark Aroclor, a bitumen, anasphaltite, a wax for example, beeswax or a mineral wax such as paraffinwax or montan wax, or a chlorinated mineral wax, or a microcrystallinewax such as those available under the registered trademark MikrovanWax." Compositions comprising such resinous or waxy carriers arepreferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organicfluid, including a liquefied normally vaporous or gaseous material, or avaporous or gaseous material, and can be solvents or nonsolvents for theactive material. For example, the horticultural petroleum spray oilsboiling in the range of from abut 275 to about 575F., or boiling in therange of about 575 to about 1,000F. and having an unsulfonatable residueof at least about 75 percent and preferably of at least about 90percent, or mixtures of these two types of oil, are particularlysuitable liquid carriers.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carrier. One or more carriers, moreover, can be usedin combination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about percent toabout 90 percent by weight of the active ingredient, preferably fromabout 20 to about 80 wt. percent. These concentrates can be diluted withthe same or different carrier to a concentration suitable forapplication. The compositions of this invention may also be dilutecompositions suitable for application. In general, concentrations ofabout 0.1 to about l0 percent by weight, of active material based on thetotal weight of the composition are satisfactory, although lower andhigher concentrations can be applied if necessary.

The compositions of this invention can also be formulated as dusts.These comprise an intimate admixture of the active ingredient and afinely powdered solid carrier such as aforedescribed. The powderedcarriers can be oil-treated to improve adhesion to the surface to whichthey are applied. These dusts can be concentrates, in which case ahighly sorptive carrier is preferably used. These require dilution withthe same or a different finely powdered carrier, which can be of lowersorptive capacity, to a concentration suitable for application. v

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the active ingredient mixed with adispersing, i.e., deflocculating or suspending agent, and if desired, afinely divided solid carrier and/or a wetting agent. The activeingredient can be in particulate form or adsorbed on the carrier andpreferably constitutes at least about 10 percent, more preferably atleast about 25 percent, by weight of the composition. The concentrationof the dispersing agent should in general be between about 0.5 percentand about 5 percent by weight of the total composition, although largeror smaller amounts can be used if desired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e.. deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can alsopossess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or

a synthetic polymeric material such as polyvinyl alcohol and methylcellulose. Preferably, however, the dispersants or dispersing agentsused are sodium or calcium salts of high molecular weight sulfonicacids, as for example, the sodium or calcium salts of lignin sulfonicacids derived from sulfite cellulose waste liquors. The calcium orsodium salts of condensed aryl sulfonic acid, for example, the productsknown as Tamol 731, are also suitable.

The wetting agents used can be nonionic type surfactants, as forexample, the condensation products of fatty acids containing at least12, preferably 16 to 20, carbon atoms in the molecule, or abietic acidor naphthenic acid obtained in the refining of petroleum lubricating oilfractions with alkylene oxides such as ethylene oxide or propyleneoxide, or with both ethylene oxide and propylene oxide, as for example,the condensation product of oleic acid and ethylene oxide containingabout 6 to 15 ethylene oxide units in the molecule. Other nonionicwetting agents like polyalkylene oxide polymers, commercially known asPluronics can be used. Partial esters of the above acids with polyhydricalcohols such as glycerol, polyglycerol, sorbitol, or mannitol can alsobe used.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfonic acidscontaining at least 10 carbon atoms in a molecule, for example, thesodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate availableunder the registered trademark Teepol, sodium salts of sulfonated castoroil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier havingthe active ingredient incorporated therein are also included in thisinvention. These can be prepared by impregnating a granular carrier witha solution of the inert ingredient or by granulating a mixture ofafinely divided solid carrier and the active ingredient. The carrier usedcan consist of or contain a fertilizer or fertilizer mixture, as forexample, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active ingredient in an or ganic solvent or mixture of solvents,such as for example, alcohols; ketones, especially acetone; ethers;hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed oncrops or insects without further dilution.

' Petroleum hydrocarbon fractions used as solvent should preferably havea flash point above 73F., an example of this being a refined aromaticextract of kerosene. Auxiliary solvents such as alcohols, ketones, andpolyalkylene glycol ethers and esters can be used in conjunction withthese petroleum solvents.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions or dispersionof the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50 percent by volume, based on the total composition, tofacilitate subsequent dilution with water. Suitable organic liquidsinclude, e.g., the above petroleum hydrocarbon fractions previouslydescribed. I

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-in-water emulsions can be used,producing concentrates which canbe diluted with relatively large volumesof water for application by high volume spraying or relatively smallvolumes of water for low volume spraying. In such emulsions, the activeingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc.; or dosage level, exposuretimes, test plants used, etc., by which the compounds and/orcompositions described and claimed are prepared and/or used.

EXAMPLE 1 Preparation of 3-Phenyl-l-cyclopropylmethyl-1- methylurea Aflask was charged with N-cyclopropylmethyl-N I methylamine (5.1 g. 0.06mole), anhydrous ether (125 m1) and triethylamine (6 drops). To thisstirred solution at room temperature was added a solution ofphenylisocyanate (6.55 g, 0.055 mole) in an equal volume of ether over a1/2 hour period. White solids precipitated and the slurry was heated atreflux for 1 hour, chilled, and filtered. The product urea meltedsharply at 103C.

Analysis: cam; c. 70.56; H, 7.9; N, 13.72 Found: C. 70.41; 11.7.8 N,14.10

EXAMPLE 2 Preparation of3-(4-Chlorophenyl)-1-cyclopropylmethyl-l-methylurea 1n the same manneras described above, N-cyclopropylmethyl-N-methylamine (3.0 g, 0.035mole) was reacted with p-chlorophenylisocyanate (6.15- g, 0.04

mole) to give the product urea, m.p. ll5-l6C.

Analysis: Calcd: C, 60.5; H, 6.35; N, 11.8

Found: C, 60.15: H, 6.26; N, 12.14

EXAMPLE 3 Preparation of3-(3,4-Dichlorophenyl)-l-cyclopropylmethyl-l-methylureaN-cyclopropylmethylrN-methylamine (5.1 g, 0.06 mole) when reacted with3,4-dichlorophenylisocyanate (10.34 g, 0.055 mole) in benzene gave awhite solid,

mp l02-4C.

Analysis: Calcd: C, 52.8; H,5.l7; N, 10.25 Found: C, 53.29; H, 5.33; N,10.42

EXAMPLE 4 Preparation of 3-(3-Trifluoromethylphenyl)-1-cyclopropy|methyl-1-methylurea N-cyclopropylmethyl-N-methylamine (5.1 g,0.06 mole) was reacted with m-trifluoromethylphenylisocyanate (10 g,0.053 mole) in diethylether to yield pearl-white platelets of theproduct urea, m.p.

ll2l3C.

Analysis: Calcd: C, 57.2; H. 5.54: N. 10.25 Found: C. 57.5; H. 5.61 N.10.16

EXAMPLE 5 Preparation of 3-(3,4-Dichlorophenyl)-1-cyclopropylmethyl-l-n-propylurea The reaction betweenN-cyclopropylmethyl-N-npropylamine (5.0 g, 0.044. mole) and 3,4-dichlorophenylisocyanate (8.3 g, 0.044 mole) carried out in benzene gavethe desired product, m.p. 7377C.

Analysis:

Calcd: C, 55.47; H. 6.12; N. 9.67 Found: C, 55.8; H, 6.03; N, 9.32

EXAMPLE 6 Preparation of 3-Phenyl-3-cyclopropylmethyl-l,ldimethylureaAnalysis: Calcd: N, 12.83 Found: N, 12.62

EXAMPLE 7 Preparation 3-(3,4-Dichlorophenyl)-3- cyclopropylmethyl-l 1-dimethylurea In basically the same manner as described in the previousexample, an excess of dimethylcarbamoylchloride (7 g, 0.065 mole) wasreacted with N- (cyclopropylmethyl)-3,4-dichloroaniline(8.4 g, 0.04mole) in the presence of triethylamine (8.0 g, 0.079 mole) and benzene.The product urea was an oil.

Analysis: Calcd: N, 9.76 Found: N, 9.33

EXAMPLE 8 Preparation of N,N-Bis(-cyclopropylmethyl)-achloroacetamide Aflask was charged with N,N-bis(cyclopropylmethyl) amine (5.0 g, 0.04mole), 20 percent aqueous sodium hydroxide solution (9.7 g) and 1.2-

dichloroethane (50 ml). This mixture was cooled to -10C. with stirringand chloroacetylchloride (4.97 g, 0.044 mole) was added dropwise over 15minutes. An exothermic reaction occurred and the temperature wasmaintained at to 10C. Stirring was continued until room temperature wasattained. The organic layer was separated, washed with percent aqueoushydrochloric acid and water. and then dried with magnesium sulfate. Thesolvent was evaporated in vacuo and the residual oil distilled, b.p.90-95C./l.l mm. The product was identified by elemental analysis and byits nuclear magnetic resonance spectrum.

Analysis: Calcd: C. 59.8 H, 7.99; N. 6.94 Found: C 59.5 H. 8.59; N. 7.66

EXAMPLE 9 Preparation of N-Cyclopropylmethyl-N-ethyl-achloroacetamideChloroacetic anhydride (13.1 g, 0.077 mole) was dis- Analysis: Calcd: C.54 7 H. 8.04;. N. 7.98

Found; C; 54 7 H. 7.93; N, 7.92

EXAMPLE 10 Preparation ofN-Cyclopropylmethyl-N-n-propyl-achloroacetamide According to theprocedure of Example 8. N- cyclopropylmethyl-N-n-propylamine was reactedwith chloroacetylchloride to give the product, b.p'. 146C./1.3 mm.

Analysis: Calcd: C. 57.1: H. 8.52; N. 7.39 Found: C, 56.7; H. 8.46; N,7.04

EXAMPLE 1 1 Analysis: Calcd:

Found:

EXAMPLE 12 Preparation of N-Cyclopropy1methyl-N-n-butyl-achloroacetamide-N-Cyclopropylmethyl-N-n-butylamine was reacted with chloroaceticanhydrideaccording to the procedure of Example 9 to give the product.b.p. ll0-15C./0.45 mm.

Analysis: Calcd: C. 59.1; H. 8.92; N. 6.88 Found: C. 58.7; H. 8.53; N.7.08

EXAMPLE 13 Preparation of N-Cyclopropylmethyl-N-allyl-achloroacetamideN-Cyclopropylmethyl-N-allylamine was reacted with chloroacetylchlorideaccording to the procedure of Example 8 to give the product, b.p.90C./0.1 mm.

Calcd:

Analysis: C 57.7; Found: C. 57.7;

EXAMPLE 14 Test for Herbicidal Utility of These Compounds Representativecompounds from those prepared in the previous examples were evaluatedfor preemergence herbicidal activity. The test procedure employed was asfollows:

Two flats seeded with six crops (cotton, soybean, .tomato, corn, riceand oats) and six weeds (mustard,

morningglory, crabgrass, yellow foxtail, Johnson grass and velvet leaf)were sprayed with a formulation concertain volume of liquid and thecalculated amount of active ingredient which would give a ratecorresponding to the indicated pounds/acre. The flats were then held inthe greenhouse and a response rated after 12 days to 16 days. Responsewas rated by a scale of 01 0. The 0-10 scale is defined as: 0 no injury;1-3 slight injury; 4-6 moderate injury. plants may die; 79 severeinjury. plants will probably die; 10 all plants dead (complete kill).The results of this test as shown below are indicative that many ofthese compounds show a high degree of herbicidal activity in many weedspecies, but may remain highly tolerant of desirable crop species.

' EXAMPLE 15 Representative derivatives of the various compounds of thisinvention were evaluated for post-emergence activity. The test procedurewas as follows:

TABLE ll POST-EMERGENCE HERBICIDAL ACTIVITY OF THE COMPOUNDS OF THESUBJECT INVENTION AT 10 LBSJACRE Soy- Cot- Mng. To- Yellow Vel. Mus-Compound Name Corn bean ton Rice Glory mato Oats Cbgs JG Foxtail Leaflard 3-Phenyl-l -cyclopropylmethyl-lmethylurea 9 l l0 6 l0 l0 6 l0 6 9l0 l0 3-(3-Trifluoromelhylphenyl)-lcyclopropylmethyH-methylurea 2 8 l0 79 l0 3 9 3 9 I 9 3-(4-chlorophenyl)-l-cyclopropylmethyl-l-methylurea 4 8l 3 7 l0 3 6 9 l0 l03-(3,4-dichlorophenyl)-l-cyclopropylmethyl-l-methylurea l0 l0 l0 4 l0 l08 l0 5 9 8 l0 3-(3,4-Dichlorophenyl)-l-cycl0-propylmelhyl-l-n-propylurea 4 4 l 3 3 5 5 8 4 4 O 73-Phenyl3-c-yclopropylmethyl-l,ldimezhylurea 4 l0 l0 2 l0 l0 3 9 9 9 9l0 3-(3,4-Dichlorophenyl)-3-cyclo propylmethyl'l,'l-dimelhylurea 6 8 4 1l0 9 l0 l0 l0 9 9 l0 N-cycl0propylmethyl-Nethyl-achloroacetamide l 4 l03 2 8 3 3 l 2 3 l N-cycl0propylmethyl-N-n-propyl-achloroacetamide 4 5 45 3 l0 5 l0 l0 8 l0 9 N-cyclopropylmethyl-N-iso propylva-chloroacetamide l 3 2 2 l 5 2 2 2 3 0 0N-cyclopropylmethyl-N-n-bulyl-achloroacetamide 2 5 5 3 3 9 2 6 7 6 2 3N,N-bis(cyclopropylmethyl)-a chloroacclamide 4 6 4 5 5 9 8 I0 9 l0 l0 l0N-cyclopropylmcthyl-N-allyl-achloroacetamide 2 4 9 l 2 9 4 5 2 3 6 3What is claimed is: l. A compound of the formula in which R is C -Calkyl, cyclopropyl methyl or allyl. .2. A compoundaccording to claim 1,which is N- cyclopropyl-methyl-N-ethyl-a-chloroacetamide.

cyclopropyl-methyl-N-n-butyl-a-chloroacetamide.

6. A compound according to claim 1, which is N,N-

35 bis(cyclopropylmethyl)-a-chloroacetamide.

7. A compound according to claim 1, which is N-cyclopropyl-methyl-N-allyl-a-chloroacetamide.

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1, whichis N-cyclopropyl-methyl-N-ethyl- Alpha -chloroacetamide.
 3. A compoundaccording to claim 1, which is N-cyclopropyl-methyl-N-n-propyl- Alpha-chloroacetamide.
 4. A compound according to claim 1, which isN-cyclopropyl-methyl-N-iso-propyl- Alpha -chloroacetamide.
 5. A compoundaccording to claim 1, which is N-cyclopropyl-methyl-N-n-butyl- Alpha-chloroacetamide.
 6. A compound according to claim 1, which isN,N-bis(cyclopropylmethyl)- Alpha -chloroacetamide.
 7. A compoundaccording to claim 1, which is N-cyclopropyl-methyl-N-allyl- Alpha-chloroacetamide.